Reactions of sodium acetylide with alkyl halides



I butyl ether, and dioxane.

United States Patent Patented Aug. 5, 19*58 REACTIQNS OF SODlUlVl ACETYLIDE WITH ALKYL HALIDES Application December 13, 1955 Serial No. 552,712

7 Claims. (Cl. 260678) N Drawing.

This invention relates to improvements in the method of effecting the reaction of sodium acetylide with alkyl halides, and more specifically to an eflicient method of reacting sodium acetylide with alkyl halides in certain organic diluents or reaction media.

The conventional methods of reacting sodium acetylide and an alkyl halide in liquid ammonia have been ex tensively reviewed by Nieuwland and Vogt (The Chemistry of Acetylene, 1945, pages 7480) and by Vaughn et al. (J. Org. Chem., 2, l22, 1937-8). These methods, however, have objectionable features which are well known in the art and which are due largely to the presence of ammonia. Liquid ammonia is difiicult to handle; it forms undesirable by-products; and in reactions utilizing alkyl halides with relatively large carbon chain lengths, the ammonia is necessarily subjected to elevated temperatures and superatmospheric pressures, thus creating reaction conditions which are admittedly hazardous. When the liquid ammonia is diluted with organic liquids such as diethyl ether, dichlorodiethyl ether, and ethylene diamine, yields of l-alkynes are greatly reduced.

The reaction of alkyl halides with sodium acetylide has also been studied to some extent using the conventional organic diluents as reaction media, e. g., Xylene, n-

But in such instances, the alkyl halides have failed to react Wtih sodium acetylide.

One object of this invention is to provide an improved method of reacting sodium acetylide with alkyl halides; another object is to effect the reaction of sodium acetylide with alkyl halides in a selective reaction medium at favorable temperatures and pressures; and a further object is to provide a rapid and efiicient reaction for producing l-alkynes.

in accordance with the invention, an alkyl halide is reacted with a dispersion of finely divided sodium acetylide, advantageously consisting mostly of particles less than 25 microns in diameter, in a selective organic liquid which is substantially inert with respect to the reactants and products of reaction, under controlled temperature conditions, to produce the desired alkyne. In a preferred and especially advantageous embodiment of the invention, the sodium acetylide is prepared according to the process of the copending application of Thomas F. Rutledge and Alio J. Buselli, Serial No. 391,139, filed November 9, 1953, and now Patent No. 2,777,884, Process For Producing Sodium Acetylide and Improved Sodium Acetylide Product. The sodium acetylide prepared by the process of he Rutledge et a1. application can be at least 95% pure, containing less than around 1% of either or both sodium hydroxide and sodium carbonate, and is characterized principally by being a virtually white, free flowing powder, mainly less than 5 microns in diameter, which can be wetted by inert liquids without undesirable coalescence of the particles. Other characteristics include high thermal and storage stabilities. For example, the sodium acetylide may be exposed to the atmosphere without spontaneous ignition, and it may be stored reaction in some manner.

for relatively long periods in dry air or inert gases such as argon or nitrogen.

I have found that certain organic liquid media have a very specific action in promoting the reaction of sodium acetylide with alkyl halides to form the desired alkynes. These diluents are NJI-dimethyl formamide, hexamethyl phosphoramide (tris-N,N-dimethyl phosphorous triamide), and l l,N-dimethyl acetamide. While the action of these organic diluents is definite, the exact manner in which they serve is not clearly understood. It may be that their action is catalytic; that some physical factors are involved, such as solubility; or that the diluents take part in the In any event it is believed that a medium of high dielectric constant is preferred since many reactions of sodium acetylide, such as alkylation via alkyl bromides, are generally regarded as being of ionic nature.

The three diluents of this invention have high dielectric constants, and are relatively inert with respect to sodium acetylide, the alkyl halides, and the reaction products. They have boiling points above the reaction temperatures of the novel process. While all three diluents have been used satisfactorily in the practice of the invention, dimethyl formamide is the most eiiective. Being a member of the series of N-alkyl amides, dimethyl formamide is a highly polar material having a dielectric constant of 26.6 (at 25 C. and 250 kc.). This is a desirable characteristic of the diluent, since the sodium acetylide reaction of this invention is regarded as being ionic in nature. Further, dimethyl formamide is relatively stable up to its atmospheric boiling point (153 C.); and above 350 C., degradation may occur to dimethylamine and carbon dioxide. it has an ignition temperature of 445 C. Fortunately it is now commercially available at a reasonable price. Since dimethyl formamide is the most eliective diluent, readily available, and the least expensive, the majority of the reactions were carried out in a medium comprising dimethyl formamide.

When reacting the improved sodium acetylide with an alkyl halide in the reaction media of this invention, excellent yields of alkynes are obtained according to the reaction:

wherein R is an alkyl and X is a halide, and the alkyl halide reacts with the sodium acetylide dispersed in the reaction medium to form the desired l-alkyne and sodium halide.

Briefly, sodium acetylide is prepared according to the process of said copending application by adding a dispersion of sodium in a liquid such as di-n-butyl ether in a reactor equipped with a thermometer, heater, stirrer and acetylene inlet. Dry, purified acetylene is bubbled into the dispersion at a temperature of from C. to C. After the evolution of hydrogen has stopped, the reaction resulting in the production of sodium acetylide has been completed. The sodium acetylide is dispersed in the di-n-butyl ether in a fine state of sub-division, around 5 microns or less in diameter. The sodium acetylide thus prepared can be separated from the reaction medium by some conventional means (such as filtration or centrifugation) and substantially dried, for example, by vacuum drying. The filtered and dried sodium acetylide can be stored or transported, if desired. It can then be dispersed in a reaction medium of this invention, such as N,N-dimethyl formamide, for subsequent reaction with an alkyl halide such as n-butyl bromide.

In carrying out a process of the invention, an alkyl halide is added to the suspension of sodium acetylide in one of the above-mentioned selective liquid media at a temperature of 25 C, to 50 C. and at such a rate rnercurate analysis.

desired reaction time, usually five to eight hours, the resulting mixture is filtered (suction) into a chilled receiver. A Dry Ice trap on the suction flasks avoids loss xylene-DMF mixtures were examined under identical conditions, and the results were similar when such mixtures were used in the process of this invention.

Loading of diluent, i. e., volume of organic medium of the alkyne. The filtrate is fractionated to isolate the per mole of sodium acetylide,.represents another aspect l-alkyne and any unreacted alkyl halide. The reaction of the novel process. Several experiments were concnvironment must be substantially free from moisture to ducted at about 15 to 35 C., using a DMF concentraprevent decomposition of the reactants. tion of 37.5 volume percent in xylene and a 25 percent The following typical examples will serve only to ilexcess of butyl bromide. Under these conditions, optilustrate the invention more fully, and accordingly they 10 mum yield was obtained at a loading of about 2 moles are not to be construed as-limiting the scope of the inof sodium acetylide per liter of mixed diluent. Convention: version and yield were 81 mole percent.

A dispersion sodium in Xylene corresponding to In a manner similar to that described for Examples 1 0.25 mole of sodium metal, was added to 300 ml. of to 5 finely divided Sodium acetylida was Shown to Xylene m a glass reactor Whlch was eqlnpped Wlth a react readily with an alkyl halide having a relatively large stirrer, condenser, thermometer, acetylene 1nlettube, and Carbon Chain length mocmdecyl bromide The reac an eiecmc heatmg mantle The Xylene was of a tion medium was a DMF concentration of 33 volume per- @9 grade which b een fieed of and low cent in xylene; the molar ratio of sodium acetylide to bolhng mateglal dlsilufltlon' 1:116 mixture Was n-octadecyl bromide was 1:1; and the reaction temperaheated to 100 -l smnngj Dn ed Punfied ture ranged from to C. The yield of l-eicosyne 6116 gas was bubbled mm the dlsparslon at aPout 100 was 90% based on n-octadecyl bromide. These results 0 After about two hours no further evolutlon Pf indicate that the yield of l-alkyne prepared in accordance dTPgeH Was recorded y a hydrogen lf the 25 with the invention increases as the carbon chain length exit gas stream. The flow of acetylene was dlscontmued, f the alkyl group increases and the mix allowed to cool to room temperature. The The other two diluents f h invention, dimethyl sodium acetylide was separated from the reaction m tamide and hexamethyl phosphorous triamide, were found dlllfn 9 y filtratlon and $11 b$ta11tl? 1113 drled to be satisfactory as liquid media for the reaction of finevawum drymgh filtered andqned do acetyhde s0 ly divided sodium acetylide with an alkyl halide, such f fefiuspemled reactlofl md1um In a 0116 as n-butyl bromide. The yields of l-alkynes, however, liter flask q pp With a stiffer, opp f i and were not as high as those obtained when using dimethyl Watercooled reflux condenser. The size of sodium parfo mid as h reaction di ticle Was less than 5 microns in diameter. The mixture I i to b understood th hi invention i l d not a heated from about 25 qf y only the three eflective'organic diluents as defined and i Was added Over a Perlod 0f 20 mlmltes- For 8113- illustrated above, but also mixtures of these diluents with plicity, the details as to amounts of reactants, total voloth v tion l organic reaction media, In general, umes of diluents or reaction media, volume percentages the other diluents must be relatively inert with respect to of dimethyl formamide, the times of reaction, reaction sodium acetylide, the alkyl halides, and the products of temperatures, and yields of l-hexyne in mole percen- 4U reaction; and such diluents must have boiling points tages based on n-butyl bromide are tabulated below. above the reaction temperature used in the process of Table 1 Examples 1 2 3 4 5 Reaetants:

Sodium Acetylide,m0les 0.25--. 0.25 1.00 0.25 0.25.

n'butyl bromide, moles 0.25..." 0.25"... 1.25 0.25""- 0.25. Diluents:

Total volume, ml. 200 380 480 395 360.

Secondary none xylene" xylene xylene butyl other.

Primary DMFL. DMF... DM DMF DMF.

Volume percent 100 35 37.5..- 44 50.

Reaction conditions:

Time, hours Temperature, C Yield of l-hexy'ne: Mole percent 1 Dimethyl tormamide.

addition.

The data above reveals the remarkable activity and usefulness of an organic medium comprising dimethyl formarnide in promoting the reaction of sodium acetylide with n-butyl bromide. Conducting the process at atmospheric pressures and normal temperatures, commercially satisfactory yields of l-hexyne are obtained in relatively short periods (5 to 8 hours). In all the examples, total l-hexyne was confirmed by standard iodo- It is noted that solvent mixtures of dimethyl formamide and xylene or butyl ether are more effective than a solvent comprising dimethyl formamide alone. The synergistic activity between the components of such mixtures undoubtedly contributes to their usefulness as reaction media. Optimum concentrations of dimethyl fcrmamide in ether xylene or butyl ether are about 35 to by volume, for reactions at about 25 to 50 Further,- butyl ether-DMF mixtures and this invention. Representative liquid media include aromatic hydrocarbons (xylene), dialkyl ethers (di-n-hexyl carbitol), and alkyl ethers of glycols orpolyglycols (di-nbutyl carbitol). I

The invention is not limited to the specific embodiments described herein, but may be practiced in other Ways without departing from the spirit and scope of the invention is defined by the following claims.

I claim: 7

l. A process for producing a l-alkyne by effecting the reaction of sodium. acetylide with an alkyl halide which comprises reacting an alkyl halide and finely divided sodium acetylide dispersed in an organic liquid medium having a high dielectric constant and being substantially inert with respect to the reactants and products of reactants, said medium being selected from the group consisting of N,N-dimethyl form-amide, N,N-dimethyl acetamide, tris-N,N-dimethyl phosphorous triamide, and mixtures thereof, conducting the reaction at a temperature of from 15 to 50 C., and separating the l-alkyne formed from the reacting materials.

2. A process for producing a l-alkyne in accordance with claim 1 wherein the organic liquid medium comprises an amount of tris-N,N-dimethyl phosphorous triamide s'ufiicient to promote the reaction.

3. A process for producing a l-alkyne in accordance with claim 1 wherein the organic liquid medium comprises an amount of N,N-dimethy1 acetamide sufficient to promote the reaction.

4. A process for producing a l-alkyne in accordance with claim 1 wherein the dispersed sodium acetylide particles are preponderantly less than 25 microns in diameter, and the reaction is carried out in the substantial absence of any substances which interfere with said reaction.

5. A process for producing a l-alkyne in accordance with claim 1 wherein the organic liquid medium comprises an amount of N,N-dimethyl formamide sufficient to promote the reaction, and the reaction environment is substantially free of any moisture whereby decomposition of the reactants is prevented.

6. A process for producing a l-alkyne in accordance 6 said organic liquid medium is about 2 moles of sodium acetylide per 1 liter of reaction medium.

7. A process for producing a l-alkyne in accordance with claim 5 in which said amount of N,N-dimethyl formamide is about to percent by volume of said organic liquid medium.

References Cited in the file of this patent UNITED STATES PATENTS 2,146,448 Scott et al. Feb. 7, 1939 2,198,236 Vaughn Apr. 23, 1940 2,724,008 Lyon et al Nov. 15, 1955 OTHER REFERENCES with claim 5 in which the ratio of sodium acetylide to 25 1949. 

1. A PROCESS FOR PRODUCING A 1-ALKYNE BY EFFECTING THE REACTION OF SODIUM ACETYLIDE WITH AN ALKYL HALIDE WHICH COMPRISES REACTING AN ALKYL HALIDE AND FINELY DIVIDED SODIUM ACETYLIDE DISPERSED IN AN ORGANIC LIQUID MEDIUM HAVING A HIGH DIELECTRIC CONSTANT AND BEING SUBSTANTIALLY INERT WITH RESPECT TO THE REACTANTS AND PRODUCTS OF REACTANTS, SAID MEDIUM BEING SELECTED FROM THE GROUP CONSISTING OF N,N-DIMETHYL FORMMIDE, N,N-DIMETHYL ACETAMIDE, TRIS-N,N-DIMETHYL PHOSPHOROUS TRIAMIDE, AND MIXTURES THEREOF, CONDUCTING THE REACTION AT A TEMPERATURE OF FROM 15* TO 50*C., AND SEPARATING THE 1-ALKYNE FORMED FROM THE REACTING MATERIALS. 